CN102866605A

CN102866605A - Decolorable toner and process for production thereof

Info

Publication number: CN102866605A
Application number: CN2012102362116A
Authority: CN
Inventors: 青木孝安; 原誉史; 伊藤刚司; 生田真大; 宇土基成; 下草宏治; 水畑浩司
Original assignee: Toshiba TEC Corp
Current assignee: Toshiba TEC Corp
Priority date: 2011-07-08
Filing date: 2012-07-06
Publication date: 2013-01-09
Anticipated expiration: 2032-07-06
Also published as: JP5431423B2; JP2013019971A; EP2544049A1; CN102866605B; EP2544049B1; US20130011777A1; US8940468B2

Abstract

The invention discloses a decolorable toner and a process for production thereof. The process for production of a decolorable toner includes aggregating dispersed fine particles of a color material comprising at least a color-forming compound, a color-developing agent and a decoloring agent with dispersed fine particles comprising at least a binder resin comprising a polyester resin to form aggregates in an aqueous medium, adding a reactive polymer having an oxazoline group into the aqueous medium, and fusing the aggregates in the aqueous medium.. As a result, it becomes possible to produce a decolorable toner which suppresses the generation of fine powder due to the release of fine particles of an erasable color material from the toner.

Description

The toner that can decolour and manufacture method thereof

Technical field

The present invention relates generally to a kind of toner, toner that particularly can decolour or eliminable and manufacture method thereof.

Background technology

Because the generally use of computing machine, software and network, becoming can promote and the sharing information processing.Fundamentally, the digitizing of information is suitable for the storage of information, accumulation, retrieval etc., and the paper medium is suitable for the demonstration (particularly observability) of information and transmits.Therefore, present state is that along with the progress of information digitalization, the consumption of paper constantly increases.On the other hand, by CO ₂Being reduced in the various fields of energy consumption of discharging expression is urgent demand.If can with being used for the interim demonstration of information or the paper medium recycle of transmission, then can make huge contribution to the reduction of energy consumption.JP-A 2004-42635 discloses a kind of method, wherein by heating color development and elimination with reversible thermal recording material.Yet, in the method, there is color forming composition at recording medium, therefore, described the method has the shortcoming that can not use common paper medium.JP-B 3457538 discloses a kind of eliminable toner of making by breaking method.Yet described eliminable toner has following shortcoming: in the process of melt kneading composition such as colour coupler, developer and decolorant, composition is reacted to each other, thereby reduced the density of the color of developing and also reduced decoloring reaction speed.As other manufacture methods of mediating outside the breaking method, also proposed to use the manufacture method of wet process, wherein by in aqueous medium, the fine particle of eliminable color material and the fine particle of adhesive resin etc. being assembled and fusion obtains toner (JP-A2010-191430).According to this method, the fine particle of eliminable color material and adhesive resin etc. can be mixed to condense and not by melt kneading experience mechanical shearing or high thermal history.Yet, in this method, be difficult to the fine particle of color material is incorporated in the toner fully, and find that this method provides following problem, thereby the fine particle of the color material that is discharged by toner remains in as fine powder and causes image deflects such as atomizing in the toner.When the fine particle of color material during by micropackaging, has been declared this tendency especially.

On the other hand, proposed, by using reactive polymer that toner resin is crosslinked, mainly improved flexibility, thermal characteristics and the mechanical property (JP-A2004-163854 and JP-A2010-48954) of toner.

Summary of the invention

The objective of the invention is so that make the toner (decolorable toner) that can decolour, it has suppressed to discharge from toner because of the fine particle of eliminable color material the generation of the fine powder that causes.

The invention provides a kind of toner that decolours, it comprises the adhesive resin that contains vibrin, color-forming compounds (color-forming compound), developer (color-developing agent) and decolorant; And have a cross-linked coating by making described adhesive resin and tool have the polymer reaction of oxazoline group to form, institute's oxazoline group of stating can with described vibrin reaction.

The present invention also provides the method for the manufacture of the toner that can decolour, described method comprises: make the dispersion fine particle of the color material that comprises at least color-forming compounds, developer and decolorant and the dispersion fine particle that comprises at least the adhesive resin that contains vibrin assemble to form aggregation in aqueous medium, adding tool in the described aqueous medium has the reactive polymer of oxazoline group, and makes afterwards the described aggregation fusion in the described aqueous medium.

Description of drawings

Fig. 1 shows the general arrangement of the imaging device (image forming apparatus) that can use according to the developer of embodiment.

Fig. 2 is the partial cross section figure be used to the imaging device of the position relationship that processing (or toner) box and device are shown.

Fig. 3 illustrates the perspective schematic view that four looks are processed the layout of (or toner) box.

Fig. 4 is the sectional view that the structure of the processing unit (box) that comprises several treating apparatus that arrange around photosensitive drum is shown.

Fig. 5 is the skeleton view of the processing unit (box) that only comprises developing apparatus.

Embodiment

Hereinafter, preferred embodiment be described more specifically the present invention with reference to it.In following explanation, except as otherwise noted, otherwise " part " and " % " that expression forms all represents with weight.

(adhesive resin)

Among the present invention used adhesive resin be can with the crosslinked vibrin of the oxazoline group of reactive polymer described later.Especially, by to the dicarboxylic acid composition with diol component carries out esterification and the vibrin of following polycondensation to obtain is preferred.The example of acid composition comprises aromatic dicarboxylic acid such as terephthalic acid (TPA), phthalic acid and m-phthalic acid; With aliphatic carboxylic acid such as fumaric acid, maleic acid, succinic acid, hexane diacid, decanedioic acid, glutaric acid, heptandioic acid, oxalic acid, malonic acid, citraconic acid and itaconic acid.

The example of alcohol composition comprises aliphatic diol such as ethylene glycol, propylene glycol, BDO, 1,3-BDO, 1,5-PD, 1,6-hexanediol, neopentyl glycol, propylene glycol (trimethylene glycol), trimethylolpropane and pentaerythrite; Alicyclic diol such as Isosorbide-5-Nitrae-cyclohexanediol and 1,4-CHDM; And the ethylene oxide adduct of bisphenol-A or propylene oxide adduct, etc.

In addition, can be by using the above polyvalent carboxylic acid's composition of trivalent or the above polyol component of ternary, such as 1,2,4-benzene tricarbonic acid (trimellitic acid) or glycerine and with above-mentioned polyester conversion, thereby make it have cross-linked structure.

Vibrin can be crystallization or unbodied, but preferably unbodied.

Can mix and use two or more vibrin with different compositions, and preferred the mixing used two or more vibrin sometimes.Particularly preferably mix and use two or more amorphous polyester resins.

The glass transition temperature of vibrin is preferably more than 45 ℃ and below 70 ℃, more preferably more than 50 ℃ and below 65 ℃.Glass transition temperature is lower than 35 ℃ vibrin not to be expected, because the heat-resisting storage stability of toner descends, in addition, becomes obvious wiping the gloss of opisthogenesis from resin.It is not preferred that glass transition temperature is higher than 70 ℃ vibrin, because low-temperature fixability descends, and also variation of the erasability during heating.From with the bridging property of oxazoline group and the easiness of emulsification, acid number is 5 to 35mgKOH/g, particularly 15 to 35mgKOH/g vibrin is preferred.

(color-forming compounds)

Color-forming compounds is that the electronics for the pigment of expression character, numeral etc. gives precursor (to the electronics precursor, electron-donating precursor).Give colour coupler as electronics, can mainly use leuco dye (leuco dye).Leuco dye is that the electronics that can form by the effect of developer color gives compound.The example comprises diphenyl methane phthalide, Phenylindole base phthalide, indyl phthalide, diphenyl methane azepine phthalide, Phenylindole base azepine phthalide, fluorane, styrene and quinoline and diaza-rhodamine lactone.

Its instantiation comprises 3, two (to the dimethylaminophenyl)-6-dimethylamino phthalides of 3-, 3-(4-diethylamino phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl) phthalide, 3, two (1-normal-butyl-2 methyl indole-3-yl) phthalides of 3-, 3, two (2-ethoxy-4-diethylamino the phenyl)-4-azepine phthalides of 3-, 3-(2-ethoxy-4-diethylamino phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine phthalide, 3-[2-ethoxy-4-(N-ethylaniline base) phenyl]-3-(1-Ethyl-2-Methyl indol-3-yl)-4-azepine phthalide, 3,6-diphenyl amino fluorane, 3,6-dimethoxy fluorane, 3,6-two n-butoxy fluoranes, 2-methyl-6-(N-ethyl-N-p-methylphenyl is amino) fluorane, 2-N, N-dibenzyl amino-6-diethylamino fluorane, the amino fluorane of 3-chloro-6-cyclohexyl, the amino fluorane of 2-methyl-6-cyclohexyl, the amino fluorane of 2-(2-chloroanilino)-6-di-n-butyl, 2-(3-trifluoromethylbenzene amido)-6-diethylamino fluorane, 2-(methylphenylamine base)-6-(N-ethyl-N-p-methylphenyl is amino) fluorane, 1,3-dimethyl-6-diethylamino fluorane, 2-chloro-3-methyl-6-diethylamino fluorane, 2-anilino--3-methyl-6-diethylamino fluorane, the amino fluorane of 2-anilino--3-methyl-6-di-n-butyl, 2-xylidino-3-methyl-6-diethylamino fluorane, 1,2-phenyl-6-diethylamino fluorane, 1,2-benzyl-6-(N-ethyl-N-isobutylamino) fluorane, 1,2-benzyl-6-(N-ethyl-N-isopentyl is amino) fluorane, 2-(3-methoxyl-4-dodecyloxy styryl) quinoline, spiral shell [5H-(1) chromene (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran]-3'-ketone, 2-(diethylamino)-8-(diethylamino)-4-methyl-, spiral shell [5H-(1) chromene (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran]-3'-ketone, 2-(di-n-butyl is amino)-8-(di-n-butyl is amino)-4-methyl-, spiral shell [5H-(1) chromene (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran]-3'-ketone, 2-(di-n-butyl is amino)-8-(diethylamino)-4-methyl-, spiral shell [5H-(1) chromene (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran]-3'-ketone, 2-(di-n-butyl is amino)-8-(N-ethyl-N-isopentyl is amino)-4-methyl-, spiral shell [5H-(1) chromene (2,3-d) pyrimidine-5,1'(3'H) isobenzofuran]-3'-ketone, 2-(di-n-butyl is amino)-8-(di-n-butyl is amino)-4-phenyl, 3-(2-methoxyl-4-dimethylaminophenyl)-3-(1-butyl-2 methyl indole-3-yl)-4,5,6, the 7-Rabcide, 3-(2-ethoxy-4-diethylamino phenyl)-3-(1-Ethyl-2-Methyl indol-3-yl)-4,5,6,7-Rabcide and 3-(2-ethoxy-4-diethylamino phenyl)-3-(1-amyl group-2 methyl indole-3-yl)-4,5,6,7-Rabcide.Its other example comprises pyridine compounds, quinazoline compound and two quinazoline compound.Can also be by mixing its two or more these compounds that use.

(developer)

Developer be by with the interaction of color-forming compounds so that the electronic receiving compound of colour coupler colour developing.In addition, thus electronics accept developer and have effect to the leuco dye contribution proton colour developing that gives colour coupler as electronics.

The example of developer comprises phenol, the slaine of phenol, the slaine of carboxylic acid, aromatic carboxylic acid, aliphatic carboxylic acid with 2 to 5 carbon atoms, benzophenone, sulfonic acid, sulphonic acid ester, phosphoric acid, the slaine of phosphoric acid, acid phosphoric acid ester, the slaine of acid phosphoric acid ester, phosphorous acid, the slaine of phosphorous acid, single phenol, polyphenol, 1,2,3-triazoles and derivant thereof.

With respect to every part of leuco dye, preferably with 0.5 to 10 part, particularly 1 to 5 part amount is used developer.If its amount is less than 0.5 part, the density of the color of then developing descends, and if its amount surpass 10 parts, then becoming is difficult to remove fully color.

(decolorant)

Used decolorant can comprise known compound among the present invention in three composition systems of leuco dye (color-forming compounds), developer and decolorant, as long as described compound suppresses coloring reaction between leuco dye and the developer by heating, thereby so that described system is colourless gets final product.

As decolorant, the disclosed temperature hysteresis that can utilize decolorant forms decolorant painted and the decolouring system and has the excellent especially performance of immediately wiping in JP-A 60-264285, JP-A 2005-1369 and JP-A 2008-280523.When the potpourri of this three composition systems that will be in colored state is heated to specific bleaching temperature Th when above, potpourri can be decoloured.In addition, even the potpourri of decolouring is cooled to the temperature that is lower than Th, also keep decolored state.When the temperature of further reduction system, below specific secondary color temperature T c, recover the coloring reaction between leuco dye and the developer, and system returns to colored state.By this way, can cause reversible painted and decoloring reaction.Especially, preferably, decolorant used among the present invention satisfies following relationship: Th〉Tr〉Tc, wherein Tr represents room temperature.

The example that can cause the decolorant of this temperature hysteresis comprises alcohol, ester, ketone, ether and sour acid amides.

Particularly preferably be ester.Its instantiation comprises the ester of the carboxylic acid of the aromatic ring that comprises replacement; comprise the carboxylic acid of unsubstituted aromatic ring and the ester of aliphatic alcohol; the ester that in each molecule, comprises the carboxylic acid of cyclohexyl; the ester of fatty acid and unsubstituted aromatic alcohol or phenol; the ester of the aliphatic alcohol of fatty acid and branching, the ester of the aliphatic alcohol of dicarboxylic acid and aromatic alcohol or branching, cinnamic acid dibenzyl ester; the stearic acid heptyl ester; didecyl adipate, hexane diacid two lauryls, hexane diacid two myristins; hexane diacid two cetyl; hexane diacid distearyl acyl group ester, laurin, myristin; glyceryl tristearate, two myristic acid glyceride and distearins.Can also be by mixing its two or more these compounds that use.

With respect to every part of leuco dye, preferably with 1 to 500 part, particularly 4 to 99 parts amount is used decolorant.If its amount then is difficult to show complete decolored state less than 1 part, and if its amount surpass 500 parts, the density of the color of then developing may descend.

According to preferred embodiment, the fine particle (or source particles to be assembled) of color material that comprises above-mentioned three kinds of compositions of leuco dye, developer and decolorant is used as nuclear and packed.The example of method for packing comprises interfacial polymerization, coacervation, situ aggregation method, submergence seasoning and submergence curing rubbing method.

Especially, preferred use wherein with melamine resin as the situ aggregation method of shell component, wherein with urethane resin as the interfacial polymerization of shell component etc.

In position in the situation of polymerization, at first, with above-mentioned three kinds of compositions dissolving and mix, then, in the aqueous solution of water-soluble polymers or surfactant with the emulsifying mixture of gained.Afterwards, to the aqueous solution of wherein adding the melamino-formaldehyde prepolymer, heat subsequently to carry out polymerization, can realize thus encapsulation.

In the situation that interfacial polymerization, with above-mentioned three kinds of compositions and the dissolving of polyvalent isocyanate prepolymer and mix, then in the aqueous solution of water-soluble polymers or surfactant with the emulsifying mixture of gained.Afterwards, to wherein adding polyacidic base such as diamines or glycol, heat subsequently to carry out polymerization, can realize thus encapsulation.

By this way, can obtain that (measure particle size range: the median particle diameter based on volume that 0.05 –, 3000 μ m) records is 0.5 to 3.5 μ m, and preferred 1.0 to 3.0 μ m also have the aqueous liquid dispersion of the encapsulation fine particle (perhaps source particles to be assembled) of the color material that sharp-pointed particle diameter distributes by laser method.As mentioned above, by encapsulating the fine particle of eliminable color material, exist in the mode that in each capsule, is in contact with one another so that consist of three kinds of compositions of leuco dye (color-forming compounds), developer and decolorant of the fine particle of color material, and do not insert adhesive resin betwixt.Therefore, formed realize the high colored state of density and the quick conversion between the decolored state painted-the decolouring system.

(release agent)

In toner of the present invention, can incorporate release agent into as required.The example of release agent comprises aliphatic hydrocarbyl wax such as low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin copolymer, polyolefin-wax, paraffin and Fischer-Tropsch synthetic wax, and their modified product; Vegetable wax such as candelila wax, Brazil wax, Japan tallow, jojoba wax and rice wax (rice wax); Animal wax such as beeswax, lanocerin and fine jade wax; Mineral wax such as montan wax, ceresine and pure white ceresine; Fatty acid amide such as linoleic acid acid amides, oleamide and lauric amide; Functionality synthetic wax and organic silica-based wax.

In the present invention, particularly preferably be, release agent has ester bond between pure composition and carboxylic acid composition.The example of alcohol composition comprises higher alcohol, and carboxylic acid composition's example comprises the saturated fatty acid with straight chained alkyl; Unsaturated fatty acid such as monoenoic acid and polyenoic acid; And hydroxy fatty acid.Carboxylic acid composition's further example comprises unsaturated polyvalent carboxylic acid such as maleic acid, fumaric acid, citraconic acid and itaconic acid.In addition, can also use their acid anhydrides.

From low-temperature fixability, the softening point of release agent can be 50 ℃ to 120 ℃, more preferably 60 ℃ to 110 ℃.

According to preferred embodiment, release agent is preferably as supplying with the potpourri of adhesive resin, and described adhesive resin is in as (the measurement particle size range: the median particle diameter based on volume that 0.05-300 μ m) records is the form of 50 to 500nm dispersion fine particle (source particles that perhaps will assemble) by laser method.Use as required adhesive resin, and preferred so that with respect to the dispersion fine particle of the color material in every part of final toner, the total amount of release agent and adhesive resin can be 1 to 99 part, particularly 2 to 19 parts mode is used release agent.

(charge control agent)

In the present invention, in adhesive resin, can be mixed for charge control agent of controlling frictional electrification etc.As charge control agent, can use metallic azo-compound, wherein preferred iron content, cobalt or chromium are as compound or the complex salt of metallic element, perhaps their potpourri.In addition, metallic carboxylic acid derivatives compounds be can also use, zirconium, zinc, chromium or boron wherein preferably contained as compound or the complex salt of metallic element, perhaps their potpourri.

The fine particle that contains above-mentioned adhesive resin, release agent, charge control agent etc. can be by the method described in the JP-A2010-191430, as wherein with these composition melt kneading, and as required that the material of melt kneading is coarsely crushed, as by via nozzle described potpourri being discharged from high-pressure pump resulting materials to be pulverized afterwards method; Perhaps emulsion polymerization forms.

(reactive polymer)

As the principal ingredient according to toner of the present invention, use have can with the reactive polymer as the crosslinked oxazoline group of the vibrin with carboxyl of toner binder resin.Must carry out crosslinkedly under the temperature of bleaching temperature being lower than, therefore, preferably can to the temperature of about 80 ° of C, carry out crosslinked polymkeric substance in room temperature.According to preferred embodiment, in aqueous dispersion medium, formed before or after the aggregation by the dispersion fine particle of color material and the dispersion fine particle that comprises at least the adhesive resin that contains vibrin, after preferred, adding tool has the reactive polymer of oxazoline group, and carries out cross-linking reaction with vibrin.Therefore, reactive polymer is preferably water-soluble, and preferably uses in it oxazoline group to be connected to and give water miscible main polymer chain, for example the polymkeric substance on the main chain of the homopolymer of unsaturated fatty acid such as acrylic or methacrylic acid or multipolymer.The example of commercially available prod comprises the Co. by Nippon Shokubai, " the EPOCROS WS-500 " and " EPOCROS WS-700 " that Ltd makes.

Consider the raising of sealing of fine particle of color material and the storage stability of toner, preferably use with respect to per 100 parts of polyesters adhesive resins, with 0.3 to 10.0 part, particularly the tool of the amount of 0.5 to 5.0 part (effective constituent that the reactive polymer of oxazoline group is arranged based on tool) has this reactive polymer of oxazoline group.

(aggregating agent prepared therefrom)

By adding aggregating agent prepared therefrom (aggregating agent), comprise preferred package color material the dispersion fine particle the dispersing solid fine particle and comprise at least contain vibrin adhesive resin (in addition, if before gathering, add, then also contain the reactive polymer that tool has the oxazoline group) the dispersion fine particle can preferably in the presence of surfactant, in aqueous dispersion medium, assemble.At this moment, preferably the solid content concentration in the aqueous liquid dispersion is set as 10% to 50%, particularly 20% to 30%.If the interpolation aggregating agent prepared therefrom, then preferably by with the adjustment of aqueous liquid dispersion to approximately 20 ℃ to 50 ℃ add aggregating agent prepared therefrom.

The preferred embodiment of aggregating agent prepared therefrom can comprise the cationic surfactant of organic aggregating agent prepared therefrom such as quaternary ammonium salt and polyethylene imine based form; Inorganic metal salt such as sodium sulphate, sodium chloride, lime chloride, calcium nitrate, magnesium chloride, magnesium sulphate, calcium nitrate, zinc chloride, iron chloride, iron sulfate, aluminium sulphate and aluminum chloride, and the inorganic metal salt polymkeric substance is such as poly-(aluminum chloride) and poly-(aluminium hydroxide); Inorganic ammonium salt such as ammonium sulfate, ammonium chloride and ammonium nitrate; And the above polyvalent metal complex compound of divalence.

With respect to the per 100 parts solids content that comprise the fine particle of color material and comprise the fine particle of adhesive resin, preferably with 3 to 40 parts, particularly 5 to 30 parts amount is used aggregating agent prepared therefrom.If the amount of aggregating agent prepared therefrom is less than 3 parts, then ability of aggregation may be insufficient, and if its amount surpass 40 parts, then between the accumulative phase, may produce corase particles, perhaps the charging property of gained toner may descend.

(gathering)

By under agitation above-mentioned aggregating agent prepared therefrom being added into the dispersion fine particle that comprises color material and comprising in the aqueous liquid dispersion of dispersion fine particle (in addition; tool has the reactive polymer of oxazoline group) of the adhesive resin (and release agent) that contains vibrin, and the temperature of dispersion liquid is maintained at about 25 to 50 ℃ gets off to assemble.

In addition, preferably, before interpolation tool described later has the reactive polymer of oxazoline group, can add the dispersion liquid of the resin thin particle that only comprises adhesive resin or also comprise as required charge control agent or wax to form the aggregation (to encapsulate) of the resin bed that has in its surface adhesive resin.The adhesive resin that is used for encapsulation preferably comprises vibrin.Above-mentioned color material is easy to be exposed on the surface of aggregation, and by adding by this way the resin thin particle, can improve the sealing of color material in toner.This resin thin particle comprises particle diameter less than the particle diameter of color material and does not comprise the fine particle of color material.In this resin thin particle, can incorporate as required wax etc. into, but from improving the sealing of color material, the resin thin particle preferably only comprises resin.

(reaction and fusion)

After the gathering of the dispersion fine particle that has carried out as mentioned above color material and the dispersion fine particle that comprises adhesive resin, add the reactive polymer that tool has the oxazoline group, and further as required, add the aqueous solution of fusion stabilizing agent such as polycarboxylic acid sodium.Afterwards, preferably under agitation, temperature is risen to gradually the glass transition temperature of adhesive resin to approximately 90 ℃, cause thus in the aggregate particles as the cross-linking reaction between the oxazoline group of the carboxyl of the vibrin of adhesive resin and the reactive polymer that tool has the oxazoline group, and promote the fusion of aggregate particles.When fusion temperature surpasses the complete erasure temperature of color material, forfeiture quality performance and the again chilling particle that becomes, so fusion temperature preferably is lower than the complete erasure temperature of color material.In order effectively to carry out crosslinked and fusion, preferably temperature was kept 0.5 to 5 hour in 50 to 90 ℃ scope.Subsequently, utilize water that the particle of assembling and fuse is washed and is dried, (measure particle size range: the median particle diameter based on volume that 1.0-30 μ m) records is the toner particle that decolours of 5.0 to 20 μ m by coulter counter method in acquisition thus.

Incidentally, the carboxyl of vibrin and tool have the cross-linking reaction between the oxazoline group of reactive polymer of oxazoline group to identify by the amido link of analyzing gained.More specifically, can by for example via infrared analysis (IR) at about 1650cm ^-1Under C=O or the existence of the C=N stretching vibration absorption peak existence of determining amido link.

(external additive)

In the present invention, in order to regulate flowability or the charging property of the toner particle that obtains as mentioned above, fine inorganic particle can be mixed with the amount based on toner particle with toner particle, the amount with 0.01% to 20% is carried out the outside and is added.As this fine inorganic particle, can use silicon dioxide, titania, aluminium oxide, strontium titanates, tin oxide etc. separately or with the form of its two or more potpourri.Preferably, as fine inorganic particle, from improving the viewpoint of environmental stability, use fine inorganic particle that utilizes hydrophobing agent surface-treated.In addition, except this inorganic oxide, can also outside add size 1 μ m and be following resin thin particle to improve clean-up performance.

[embodiment]

Hereinafter, with reference to embodiment and comparative example the present invention is described more specifically.

(manufacturing of amorphous polyester resin A)

Utilize nitrogen displacement to be equipped with air in the four neck flasks of nitrogen inlet tube, drainpipe, stirrer and thermopair, and place therein the polyoxygenated propylidene (2.2)-2 of 4900g, the polyoxygenated ethylidene (2.0)-2 of two (4-hydroxy phenyl) propane of 2-, 1950g, the fumaric acid of two (4-hydroxy phenyl) propane of 2-, 2088g, the hexane diacid of 292g, the tert-butyl catechol of 10g and the tin octoate of 50g.Temperature with content in blanket of nitrogen rises to 210 ℃, and so that reacts under 210 ℃.Then, so that under 8.3KPa, under reduced pressure carry out condensation reaction, until reach the softening point of expectation, obtain thus amorphous polyester resin A.The amorphous polyester resin A that obtains has 91 ℃ softening point, 51 ℃ glass transition point and the acid number of 16mgKOH/g.

(manufacturing of amorphous polyester resin B)

Utilize nitrogen displacement to be equipped with air in the four neck flasks of nitrogen inlet tube, drainpipe, stirrer and thermopair, and place therein the polyoxygenated propylidene (2.2)-2 of 4900g, the polyoxygenated ethylidene (2.0)-2 of two (4-hydroxy phenyl) propane of 2-, 1950g, two (4-hydroxy phenyl) propane of 2-, the fumaric acid of 1728g, the hexane diacid of 692g, the trimellitic anhydride of 384g, the tert-butyl catechol of 10g and the tin octoate of 50g.Temperature with content in blanket of nitrogen rises to 210 ℃, and so that reacts under 210 ℃.Then, so that under 8.3KPa, under reduced pressure carry out condensation reaction, until reach the softening point of expectation, obtain thus amorphous polyester resin B.The amorphous polyester resin B that obtains has 102 ℃ softening point, 51 ℃ glass transition point and the acid number of 33mgKOH/g.

(manufacturing of toner binder resin dispersion liquid A)

In the 5L rustless steel container, under the stirring of 200rpm, in the anionic surfactant of amorphous polyester resin B, the 40g of amorphous polyester resin A, the 210g of 25 ℃ of lower 390g of dispersion " Neopelex G-15(is made by Kao Corporation) " (neopelex) (solids content: 15wt.%), the aqueous solution of the 5wt.% potassium hydroxide of the non-ionic surfactant of 6g " Emulgen430(is made by Kao Corporation) " (polyoxygenated ethylidene (26mol) oleyl ether) and 218g, temperature is risen to 90 ℃ subsequently.Content is stabilized in 90 ℃ down and is stirring little maintenance 2 hours.Subsequently, wherein drip the deionized water of 1076g with 6g/ minute clockwise, obtain thus emulsified material.After cooling, emulsified material by metallic screen, is obtained toner binder resin dispersion liquid A thus.The median particle diameter based on volume of the resin thin particle among the toner binder resin dispersion liquid A that obtains is that 0.16 μ m and solid content concentration wherein are 32wt.%.

(manufacturing of releasing agent dispersion)

In the 1L beaker, place the alkenyl succinic acid dipotassium of the deionized water of 480g and 4.3g aqueous solution (trade name: Latemul ASK, made effective concentration by Kao Corporation: 28wt.%), and disperse therein the Brazil wax of 120g.In under the temperature with dispersion liquid remains on 90 to 95 ℃, utilize ultrasonic homogenizer (trade name: US-600T is made by Nihonseiki Kaisha Ltd.) that the gained dispersion liquid was processed 30 minutes.After with the dispersion liquid cooling, to wherein adding deionized water so that solids content is adjusted to 20wt.%, obtain thus releasing agent dispersion.The median particle diameter based on volume of the release agent in the releasing agent dispersion is 0.42 μ m.

(embodiment 1)

In order to form color material, with 5 parts the crystal violet lactones as leuco dye (CVL), 5 parts as the 4-HBA benzyl ester of developer and 50 parts the 4-benzyl oxygen base phenylethyl laurate heating and melting as bleaching temperature controlling agent (decolorant).The melted material of gained is mixed the solution that obtains and pours in 250 parts the aqueous solution of 8% polyvinyl alcohol (PVA) with the ethyl acetate with 20 parts aromatics polyvalent isocyanate prepolymer and 40 parts of passing through as the encapsulation agent, and with gained emulsifying mixture and dispersion.70 ℃ lower continue stir abouts 1 hour after, to wherein adding 2 parts water-soluble aliphatic modified amine with as reaction reagent, and remain on 90 ℃ in the temperature with liquid and further continued stir about 3 hours in lower, form thus colourless capsule particle.In addition, place refrigerating machine (under-30 ℃) with colour developing capsule particle dispersions obtained, obtain thus the dispersion of blue particles.Use is measured the median particle diameter based on volume of gained colour particles by " SALD-7000 " that Shimadzu Corporation makes, and is defined as 2 μ m.In addition, described colour particles shows 79 ℃ complete bleaching temperature Th and-20 ℃ complete painted temperature T c.

Bleaching temperature refers to show the temperature of the density of the image in the complete decolored state (therefore wherein not mutually coupling of color-forming compounds and developer does not cause the painted state that causes because of coupling) fully.Simultaneously, complete color temperature refers to show the temperature of the density of the image in the complete colored state (wherein when using when having the toner of described composition, the state that the density of image becomes almost maximum).

100 parts the dispersion liquids that contain 10 parts of above-mentioned encapsulation color materials, 283 parts toner binder resin dispersion liquid A(are contained 85 parts of resinous principles) and 25 parts releasing agent dispersion (containing 5 parts of release agent compositions) mix, and further to 11% the ammonium sulfate [(NH that wherein adds 164 parts ₄) ₂SO ₄] aqueous solution to assemble, prepare thus the toner particle dispersion liquid.Afterwards, to the aqueous solution of wherein adding the acrylic polymers contain the oxazoline group (" EPOCROSWS-700 ", by Nippon Shokubai Co., Ltd. makes, polymer content: 25%), thereby provide polymer content in 7.2% the toner to the ratio of solids content.Then, to the 2.5wt.% aqueous solution of wherein adding 250 parts anionic surfactant (" EMAL E-27C ", by Kao Corporation make), and temperature risen to 65 ℃ and kept 2 hours, prepare thus the toner dispersion liquid.After cooling, by dehydration, washing and the dry toner particle of from dispersion liquid, collecting.(aperture: 50 μ m, measure particle size range: the median particle diameter based on volume of the toner particle of the collection that 1.0 to 30 μ m) records is 6.6 μ m to use Coulter-counter.

With 3.5 parts hydrophobic silicas (" NAX50 ", by Japan Aerosil Co., Ltd. make) and 0.5 part titania (" NKT90 ", by Japan Aerosil Co., Ltd. make) mix to carry out the outside interpolation with the toner particle of 100 parts of acquisitions, obtain thus the toner of embodiment 1.

(embodiment 2)

With with embodiment 1 in identical mode prepare toner, difference is, changes the addition of " EPOCROS WS-700 " among the embodiment 1, thereby provides polymer content in 10.4% the toner to the ratio of solids content.

(embodiment 3)

With with embodiment 1 in identical mode prepare toner, difference is, changes the addition of " EPOCROS WS-700 " among the embodiment 1, thereby provides polymer content in 4.8% the toner to the ratio of solids content.

(embodiment 4)

With 100 parts contain 10 parts with embodiment 1 in the dispersion liquid, 190 parts toner binder resin dispersion liquid A(of encapsulation color material of same way as preparation contain 57 parts of resinous principles) and 25 parts releasing agent dispersion (containing 5 parts of release agent compositions) mix, and further to 11% the ammonium sulfate [(NH that wherein adds 164 parts ₄) ₂SO ₄] aqueous solution to assemble, prepare thus the nuclear particle dispersion liquid.In addition, under 50 ℃, contain 28 parts of resinous principles to wherein adding 93 parts of toner binder resin dispersion liquid A(that are used to form shell), and the potpourri former state of gained kept 3 hours, thus the toner dispersion liquid of preparation encapsulation.Afterwards, to the aqueous solution of wherein adding the acrylic polymers contain the oxazoline group (" EPOCROS WS-700 ", by Nippon Shokubai Co., Ltd. makes, polymer content: 25%), thereby provide polymer content in 3.8% the toner to the ratio of solids content.Then, to the 2.5wt.% aqueous solution of wherein adding 250 parts anionic surfactant (" EMAL E-27C ", by Kao Corporation make), and temperature risen to 65 ℃ and kept 2 hours, prepare thus toner.Afterwards, with embodiment 1 in identical mode, by dehydration, washing and the dry toner particle of collecting, and add hydrophobic silica and titania to described toner particle peripheral, obtain thus encapsulated toners.Take with embodiment 1 in the thus obtained toner that records of identical mode based on the median particle diameter of volume as 7.2 μ m.

(embodiment 5)

With 100 parts contain 10 parts with embodiment 1 in the dispersion liquid, 190 parts toner binder resin dispersion liquid A(of encapsulation color material of same way as preparation contain 57 parts of resinous principles) and 25 parts releasing agent dispersion (containing 5 parts of release agent compositions) mix, and further to 11% the ammonium sulfate [(NH that wherein adds 164 parts ₄) ₂SO ₄] aqueous solution to assemble, prepare thus the nuclear particle dispersion liquid.In addition, under 50 ℃, contain 28 parts of resinous principles to the toner binder resin dispersion liquid A(that is used to form shell that wherein adds 93 parts), and the potpourri former state of gained kept 3 hours, thus the toner dispersion liquid of preparation encapsulation.Afterwards, to the aqueous solution of wherein adding the acrylic polymers contain the oxazoline group (" EPOCROS WS-700 ", by Nippon Shokubai Co., Ltd. makes, polymer content: 25%), thereby provide polymer content in 2.8% the toner to the ratio of solids content.Then, to the 2.5wt.% aqueous solution of wherein adding 250 parts anionic surfactant (" EMAL E-27C ", by Kao Corporation make), and temperature risen to 65 ℃ and kept 2 hours, thus the toner dispersion liquid of preparation encapsulation.Afterwards, with embodiment 1 in identical mode, by dehydration, washing and the dry toner particle of collecting, and add hydrophobic silica and titania to described toner particle peripheral, obtain thus the toner of encapsulation.Take with embodiment 1 in the thus obtained toner that records of identical mode based on the median particle diameter of volume as 7.0 μ m.

(comparative example 1)

With with embodiment 1 in identical mode prepare toner, difference is, the temperature of the dispersion liquid by the toner particle that will assemble rises to 65 ℃ and be not added on " the EPOCROS WS-700 " that add among the embodiment 1 and form the toner dispersion liquid.

About following items the toner that obtains in above-described embodiment and comparative example is estimated.(toner fine powder)

Use have 50 μ m apertures the Ku Erte particle-size analyzer (measure particle size range: 1.0 to 30 μ m) measure wash, the particle diameter of each toner behind dry and outside the interpolation.Adopt the value of the cumulative amount % in 1.0 μ m to the 2.0 μ m scopes in the base distribution (based on the distribution of quantity).(storage stability of toner)

With the carrying out of 20.0g dipping 8 hours in the hot water of each toner under 50 ℃ of outside interpolation, then used " Powder Tester " vibration of being made by Hosokawa Micron Corporation 10 seconds.Afterwards, (42 orders, opening: the ratio of the amount of the toner of the gathering 0.351mm) (wt.%) is as the index of the storage stability of toner will to remain in sieve.General introduction and the evaluation result of above-described embodiment and comparative example are summed up and be illustrated in the following table 1.

Table 1

According to the result shown in the upper table 1, the polymer treatment toner particle that contains the oxazoline group by utilization, not only improved the storage stability of toner, and significantly improved the sealing of fine particle in toner particle of the color material of the toner that can decolour, but the sealing in the toner is because of micropackaging especially difficulty (comparative example 1).Also find, suppressed the generation (embodiment 1 to 3) of toner fine powder.In addition, discovery before the polymkeric substance that utilization contains the oxazoline group is processed by utilizing the shell material encapsulated toners particle that is mainly consisted of by adhesive resin, even by utilizing the polymkeric substance that contains on a small quantity the oxazoline group to process, also further improved the sealing (embodiment 4 and 5) of micropackaging fine particle in toner of the color material of the toner that can decolour.

In each toner of above-described embodiment, the complete bleaching temperature of color material is 79 ℃, and must carry out photographic fixing (fixing) being lower than under 79 ℃ the temperature.Physical strength by crosslinked enhancing toner has improved the molecular weight of resin and has also improved fixing temperature.Therefore, for form can be under colored state the toner of photographic fixing at low temperatures, preferably, only in the shell zone, namely causing crosslinked on the surface of toner and in the zone at its near surface and not in the inside at toner, namely in aggregate particles, causing cross-linking reaction.Therefore, the same with the situation of embodiment 4 and 5, preferably, after forming aggregate particles, utilize the thin layer of vibrin particle to coat the whole surface of each aggregate particles, cause afterwards cross-linking reaction.

Although the complete erasure temperature with color material changes, because the restriction of material is difficult to improve the complete erasure temperature of color material and is fully improving the poor of color temperature and erasure temperature.Given this, preferably, erasure temperature is set as 85 to 120 ℃, fixing temperature is set as approximately 85 to 70 ° of C, and the difference of erasure temperature and fixing temperature (fixing temperature) is set as more than 10 ℃.For the toner that needs as mentioned above to have low-temperature fixability, particularly importantly the same with the situation of embodiment 4 and 5, only in surf zone, carry out crosslinked.

Each toner of embodiment 1 to 5 to be placed on the MFP(" e-STUDIO3520c " that improves in order estimating, to be made by Toshiba Tec Corporation) in, and form uncertain image.Then, in the fixing device of improveing in order estimating (30mm/s), fixing temperature to be set as 75 ℃, and erasure temperature to be set as 85 ℃, and carry out the photographic fixing of toner and wipe.As a result, each toner shows sufficient fixation performance and erasability.

Fig. 1 illustrates the schematic arrangement figure that can use according to the total structure of the imaging device of the developer of present embodiment.

Go out as shown, four drum tandem type color image forming apparatus (MFP) 1 are provided with scanner section 2 and ADF section 3 at an upper portion thereof.

Color image forming apparatus 1 has the image-generating unit 11 below intermediate transport band 10.Image-generating unit 11 comprised along four forming as

unit

11Y, 11M, 11C and 11E that intermediate transport band 10 is arranged in parallel.(or erasable) blue (E) toner image that image-generating

unit

11Y, 11M, 11C and 11E form respectively yellow (Y), peony (M), blue-green (C) and can decolour.

Color image forming apparatus 1 has three kinds of imaging patterns, comprise that (1) use is selected from the pattern of the developer formation image of three kinds of color Y, M and C, (2) developer that uses Y, M and C and the toner that can decolour form the pattern of image, (3) only use the toner that to decolour to form the pattern of image, and carry out imaging by any that select these patterns.In the evaluation of the fixation performance of the toner that decolours in the above-described embodiments, by only using the toner that can decolour and only moving image-generating unit 11E and select imaging pattern (3) to carry out imaging.

Image-generating

unit

11Y, 11M, 11C and 11E have respectively

photosensitive drum

12Y, 12M, 12C and 12E as the image-bearing member.Rotate on the direction of each comfortable arrow m of

photosensitive drum

12Y, 12M, 12C and 12E.Around

photosensitive drum

12Y, 12M, 12C and 12E, be provided for charged

device

13Y, 13M, 13C and the 13E of each drum along sense of rotation, developing

apparatus

14Y, 14M, 14C and 14E and photosensitive drum clearer 16Y, 16M, 16C and 16E.

At each charged

device

13Y, 13M, 13C and 13E and each developing

apparatus

14Y, 14M, 14C and 14E, between

photosensitive drum

12Y, 12M, 12C and the 12E, utilize and be derived from the irradiation light of laser explosure device (sub-image formation device) 17 to form electrostatic latent image at

photosensitive drum

12Y, 12M, 12C and 12E.

Developing

apparatus

14Y, 14M, 14C and 14E be supplying toner on the sub-image on

photosensitive drum

12Y, 12M, 12C and the 12E.

Under tension force, configure intermediate transport bands 10 and its direction at arrow S is rotated around support roller 21, driven roller 20 and the first to the 3rd jockey pulley 22 to 24.Intermediate transport band 10 is faced and is contacted with

photosensitive drum

12Y, 12M, 12C and 12E.In the position of intermediate transport band 10 in the face of

photosensitive drum

12Y, 12M, 12C and 12E, transferring

roller

18Y, 18M, 18C and 18E are set respectively one

time.Transferring roller

18Y, 18M, 18C and a 18E are that conductive rollers and the bias voltage that will initially shift are supplied to each transfer portion.

Secondary transferring roller 27 is configured to face the secondary transferring section of the intermediate transport band 10 of being supported by support roller 21.At secondary transferring section place, the support roller 21 as conductive rollers is applied predetermined secondary transferring bias voltage.As scraps of paper P(P1 or P2) by between intermediate transport band 10 and the secondary transferring roller 27 time, with the toner image secondary transferring on the intermediate transport band 10 to scraps of paper P.After secondary transferring, 10a comes middle travelling belt 10 is cleaned by the band clearer.

Configuration is used for to the input tray 4 of the secondary transferring roller 27 supply scraps of paper below laser explosure device 17.The artificial paper feed mechanism that is used for the scraps of paper of the artificial supply of charging in the configuration of the right side of color image forming apparatus 1.

Along passage from input tray 4 to secondary transferring roller 27, arrange pick-up roller 4a,

separate roller

28a and 28b, transfer roller 28b and alignment roller to 36 to form paper feed mechanism.Along from the hand feed dish 31a of hand feed mechanism 31 to alignment roller to 36 passage, hand feed pick-up roller 31b and hand feed separate roller 31c are set.

In addition, continue to use at the vertical Transfer pipe 34 of uploading the paper feeding sheet from input tray 4 or hand feed dish 31a to the direction of secondary transferring roller 27, collocating medium sensor 39 is with the type of the scraps of paper that detect charging.Color image forming apparatus 1 is constituted can be based on the testing result that provides by medium sensor 39, the speed of the control transmission scraps of paper, transmission condition, fixing conditions etc.In addition, along vertical Transfer pipe 34, in the downstream of secondary transferring section fixing device 30 is set.By alignment roller to 36 and secondary transferring roller 27, the scraps of paper that will take out from input tray 4 along vertical Transfer pipe 34 or be sent to fixing device 30 from the scraps of paper of hand feed mechanism 31 supplies.Fixing device 30 comprises the fixing band 53 around a pair of warm-up mill 51 and driven roller 52 windings, and by the collaborative roller (mating roller) 54 of fixing band 53 with described warm-up mill 51 relative configurations.Between fixing band 53 and collaborative roller 54, transmit the scraps of paper be carried at the toner image that shifts at secondary transferring section place by warm-up mill 51 it being heated, thus with toner image to the scraps of paper.In the downstream of fixing device 30, arrange and scraps of paper P is directed to exit roller 41 or returns grid (gate) 33 on the unit 32.The scraps of paper P that is directed on the exit roller 41 is expelled to ADF section 3.Again be directed to secondary transferring roller 27 with being directed to the scraps of paper P that returns on the unit 32.

The 11E of imaging section comprises integratedly that photosensitive drum 11 is connected with treatment facility and is configured to freely be connected with the primary clustering of color image forming apparatus 1 and from its dismounting.The 11y of imaging section, 11M and 11C also have the 11 similar structures with imaging section.Illustrate in greater detail with reference to Fig. 2 to 5 pair of color image forming apparatus 1.

As shown in Fig. 2 and 3, color image forming apparatus 1 has

toner Cartridge

201Y, 201M, 201C and the 201E that is supplied to developing

apparatus

14Y, 14M, 14C and 14E for the toner with each

color.Toner Cartridge

201Y, 201M, 201C and 201E removably are installed on the imaging device 1.In order to realize the correct coupling with developing

apparatus

14Y, 14M, 14C and 14E, the toner Cartridge setting of each color has been stored

IC chip

110Y, 110M, 110C and the 110E of each colouring information of developer.

Fig. 4 is the sectional view of the 11Y of imaging section, 11M, 11C and 11E.If the 11E of imaging section is used for embodiment, then it is configured as the processing unit (box) that comprises photosensitive drum 12E, charged device 13E, developing apparatus 14E and the cleaning device 16E of integratedly combination.The 11Y of imaging section, 11M and 11C also have similar structures.

Incidentally, although Fig. 4 shows the processing unit that comprises separately around all treatment facilities (device) of photosensitive drum, only comprise the developer box that removably is installed to developing

apparatus

14Y, 14M, 14C or 14E on the color image forming apparatus (MFP) 1 but can consist of, as shown in Figure 5.

Although specific implementations of the present invention is illustrated, these embodiments are only for exemplary and be not intended to limit the scope of the invention.In fact, herein described novel embodiment can be implemented in multiple other modes; In addition, in the situation that do not deviate from spirit of the present invention, can carry out herein various omissions, the alternative and change of the form of described embodiment.Appending claims and their equivalent are intended to cover this form or the modification that drops in the scope and spirit of the present invention.

Claims

1. the toner that can decolour comprises the adhesive resin, color-forming compounds, developer and the decolorant that contain vibrin; And have a cross-linked coating by making described adhesive resin and tool have the polymer reaction of oxazoline group to form, institute's oxazoline group of stating can with described vibrin reaction.

2. toner according to claim 1, wherein, described adhesive resin, described color-forming compounds, described developer and described decolorant form aggregation, and utilize and have and can process to form cross-linked coating to described aggregation with the reactive polymer of the crosslinked oxazoline group of described vibrin.

3. toner according to claim 2, wherein, the surf zone of described aggregation only is made of described vibrin.

4. toner according to claim 1, wherein, utilize and to have and to process form cross-linked coating to the particle of the color material that comprises at least color-forming compounds, developer and decolorant with the aggregation that comprises at least the particle of adhesive resin with the reactive polymer of the crosslinked oxazoline group of vibrin.

5. each described toner in 4 according to claim 2, wherein, utilize the main shell material that is consisted of by the adhesive resin that comprises vibrin to encapsulate the particle of described color material and comprise the aggregation of the particle of described adhesive resin, and utilize tool to have the reactive polymer of oxazoline group the described vibrin in the described shell material to be carried out crosslinked to form described cross-linked coating.

6. each described toner in 5 according to claim 1, wherein, the particle of described color material is micropackaging.

7. method for the manufacture of the toner that can decolour, described method comprises: make the dispersed particle of the color material that comprises at least color-forming compounds, developer and decolorant and the dispersed particle that comprises at least the adhesive resin that contains vibrin assemble to form aggregation in aqueous medium, in described aqueous medium, add the reactive polymer that tool has the oxazoline group, and afterwards with the described aggregation fusion in the described aqueous medium.

8. method according to claim 7, further comprise: after forming described aggregation and before the interpolation tool has the described reactive polymer of oxazoline group, by add comprise at least adhesive resin the dispersion fine particle to be attached to described aggregation, encapsulate described aggregation thereby coat described aggregation with it.

9. according to claim 7 or 8 described methods, wherein, the particle of described color material is micropackaging.

10. each described method in 9 according to claim 7 wherein, is carried out described gathering under the temperature of the complete bleaching temperature of the particle that is lower than described color material.

11. a toner Cartridge comprises according to claim 1 each described toner in 6.

12. a handle box comprises: photosensitive at least member and comprise according to claim 1 the developing apparatus of each described toner in 6.

13. an imaging device comprises according to claim 1 each described toner in 6.